Methods for producing basestocks from renewable sources using dewaxing catalyst

ABSTRACT

Provided are methods for producing a lube base stock and/or a fuel from a feedstock of biological origin, the method including: contacting the feedstock in the presence of a catalyst to produce a lube base stock and/or a fuel, wherein the catalyst comprises: a zeolite component selected from a zeolite having 10-member ring pores, a zeolite having 12-member ring pores and a combination thereof, 0.1 to 5 weight % of a hydrogenation component selected from Pt, Pd, Ag, Ni, Co, Mo, W, Rh, Re, Ru, Ir and a mixture thereof, and a hydrothermally stable binder component.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser.No. 61/782,620 filed Mar. 14, 2013 and is herein incorporated byreference in its entirety.

FIELD

The present disclosure relates to catalysts for use in dewaxing andother hydrocarbon conversion processes and methods of using suchcatalysts. Specifically, this disclosure relates to a dewaxing catalystcomprising a zeolite component, a metal component for promotinghydrogenation and a hydrothermally stable binder component, and methodsof using such catalysts.

BACKGROUND

Waxy feedstocks may be used to prepare basestocks having a highviscosity index (VI). However, in order to obtain a basestock having thelow temperature properties suitable for most uses, it is usuallynecessary to dewax the feedstock. Dewaxing may be accomplished by meansof a solvent or catalytically. Solvent dewaxing is a physical processwhereby waxes are removed by contacting with a solvent, such as methylethyl ketone, followed by chilling to crystallize the wax and filtrationto remove the wax. Catalytic dewaxing involves chemically converting thehydrocarbons leading to unfavorable low temperature properties tohydrocarbons having more favorable low temperature properties. Longchain normal paraffins and slightly branched paraffins readily solidifyand thus result in generally unfavorable low temperature properties.Catalytic dewaxing is a process for converting these long chain normalparaffins and slightly branched paraffins to molecules having improvedlow temperature properties.

Catalytic dewaxing may be accomplished using catalysts that functionprimarily by cracking waxes to lower boiling products, or by catalyststhat primarily isomerize waxes to more highly branched products.Catalysts that dewax by cracking decrease the yield of lubricating oilswhile increasing the yield of lower boiling distillates. Catalysts thatisomerize do not normally result in significant boiling pointconversion. Catalysts that dewax primarily by cracking are exemplifiedby the zeolites ZSM-5, ZSM-11, ZSM-12, beta and offretite. Catalyststhat dewax primarily by isomerization are exemplified by the zeolitesZSM-22, ZSM-23, SSZ-32, ZSM-35, ZSM-48 and ZSM-50. To ensure adequatemechanical strength for use in a dewaxing reactor, such zeolitecatalysts are generally combined with an inorganic oxide binder, such asalumina.

Catalysts are needed for the upgrading of renewable basestocks for fuelsand lubricant applications. For example, a catalyst for fatty acidcoupling helps production of a highly flexible feedstock. As shown inFIG. 1, this feedstock can then be hydrogenated and/or isomerized usingconventional refinery processing, thereby producing high value productsconsisting of a mixture of fuels, high viscosity, and low viscositylubricants. This product stream can easily be separated usingconventional fractionation and distillation equipment.

The hydrogenation/isomerization catalyst for renewable feedstocks hasseveral challenges to deal with: 1) a highly oxygenated feed (10%oxygen), 2) high heats of reaction, and 3) generation of water which isconverted into steam in the reactor. The last challenge is of majorconcern to current dewaxing catalysts because steam can cause issueswith the hydrothermal stability of the catalyst and can causedeactivation by dealuminating the zeolite catalyst and/or degradation ofthe oxide support/binder leading to agglomeration of the metal.

Conventional dewaxing catalysts are, however, susceptible to poisoningby contaminants in a feedstock. To mitigate the problem of catalystpoisoning and to allow effective dewaxing of feedstocks with very highlevels of waxy materials, it is often desirable to be able to maximizethe dewaxing activity of the catalyst. However, in seeking maximizeactivity, it is also important to maintain the mechanical strength ofthe catalyst.

U.S. Pat. No. 8,263,517 to Christine N. Elia describes a dewaxingcatalyst comprising a zeolite with a low silica to alumina ratio incombination with a low surface area binder. The low surface area binderis believed to increase access to the active sites of the zeolite.Especially for bulky feeds, increased access to zeolite active sites isexpected to lead to an overall increase in activity.

U.S. Patent Publication No. 2011/0192766 mentions a supported catalystcomprising a zeolite having a silica to alumina molar ratio of 500 orless, a first metal oxide binder having a crystallite size greater than200 Å and a second metal oxide binder having a crystallite size lessthan 100 Å, wherein the second metal oxide binder is present in anamount less than 15 wt % of the total weight of the catalyst.

SUMMARY

The present disclosure relates to catalysts for use in dewaxing andother hydrocarbon conversion processes and methods of using suchcatalysts. In an embodiment, there is provided a method for producing alube base stock and/or a fuel from a feedstock of biological origin, themethod comprising: contacting the feedstock in the presence of acatalyst to produce a lube base stock and/or a fuel, wherein thecatalyst comprises: a zeolite component selected from a zeolite having10-member ring pores, a zeolite having 12-member ring pores and acombination thereof, 0.1 to 5 weight % of a hydrogenation componentselected from Pt, Pd, Ag, Ni, Mo, Co, W, Rh, Re, Ru, Ir and a mixturethereof, and a hydrothermally stable binder component selected fromsilica, alumina, silica-alumina, titania, zirconia, tantalum oxide,tungsten oxide, molybdenum oxide, vanadium oxide, magnesium oxide,calcium oxide, yttrium oxide, lanthanum oxide, cerium oxide, niobiumoxide, tungstated zirconia, cobalt molybdenum oxide, cobalt molybdenumsulfide, nickel molybdenum oxide, nickel molybdenum sulfide, nickeltungsten oxide, nickel tungsten sulfide, cobalt tungsten oxide, cobalttungsten sulfide, nickel molybdenum tungsten oxide and nickel molybdenumtungsten sulfide, cobalt molybdenum tungsten oxide and cobalt molybdenumtungsten sulfide, wherein the weight ratio of the zeolite to thehydrothermally stable binder is 85:15 to 25:75.

In another embodiment, there is provided a method for producing a lubebasestock and/or a fuel from a feedstock of biological origin, themethod comprising: contacting the feedstock in the presence of acatalyst to produce a lube base stock and/or a fuel, wherein thecatalyst comprises: a zeolite selected from ZSM-48, ZSM-23, ZSM-50,ZSM-5, ZSM-22, ZSM-11, ferrierite, faujasite, beta, ZSM-12, MOR, and amixture thereof, and a hydrogenation component comprising at least threemetals selected from the group consisting of Pt, Pd, Ag, Ni, Mo, Co, W,Rh, Re, and Ru, wherein at least one of the at least three metals is ineither an oxide or sulfide form. In an aspect of the present embodiment,the catalyst further comprises a binder component.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a scheme illustrating process flow schematic for theconversion of renewable feedstocks to higher value fuels and lubesproducts where a catalyst of the present disclosure can be placed intothe hydroisomerization unit.

FIG. 2 is a scheme illustrating process chemistry for the conversion ofrenewable feedstocks.

DETAILED DESCRIPTION

All numerical values within the detailed description and the claimsherein are modified by “about” or “approximately” the indicated value,and take into account experimental error and variations that would beexpected by a person having ordinary skill in the art.

The present disclosure provides a method for producing a lube base stockand/or a fuel from a feedstock of biological origin, the methodcomprising: contacting the feedstock in the presence of a catalyst toproduce a lube base stock and/or a fuel, wherein the catalyst comprisesa zeolite, a metal for promoting hydrogenation and a hydrothermallystable binder. In various embodiments, the zeolite is selected fromselected from a zeolite having 10-member ring pores, a zeolite having12-member ring pores and a combination thereof; the metal component isselected from the group consisting of Pt, Pd, Ag, Ni, Mo, W, Rh, Re, Ruand a mixture thereof; and the hydrothermally stable binder is selectedfrom silica, alumina, silica-alumina, titania, zirconia, tantalum oxide,tungsten oxide, molybdenum oxide, vanadium oxide, magnesium oxide,calcium oxide, yttrium oxide, lanthanum oxide, cerium oxide, niobiumoxide, tungstated zirconia, cobalt molybdenum oxide, cobalt molybdenumsulfide, nickel molybdenum oxide, nickel molybdenum sulfide, nickeltungsten oxide, nickel tungsten sulfide, cobalt tungsten oxide, cobalttungsten sulfide, nickel molybdenum tungsten oxide and nickel molybdenumtungsten sulfide, cobalt molybdenum tungsten oxide and cobalt molybdenumtungsten sulfide. The catalysts provided herein have improvedhydrothermal stability of the dewaxing catalysts which are, for example,used in conversion of renewable basestock. Also, the catalysts canminimize metal agglomeration, thereby improving catalytic selectivityand activity.

As shown in FIG. 2, a solid base catalyst such as La/ZrO₂ convertsnatural oils via coupling reactions to ketone or acid functionalizedfeedstocks. The catalyst of the present disclosure is used in the nextstage and is capable of doing the hydrogenation and/or isomerization inthe presence of water and CO₂ without significantly cracking themolecules to gaseous products.

In various embodiments, a weight ratio of the zeolite to thehydrothermally stable binder can be controlled. In an embodiment, forexample, the weight ratio of the zeolite to the hydrothermally stablebinder is 85:15 to 25:75, particularly, 80:20 to 65:35. In particularembodiments, the ratio is 80:20 or 65:35.

In another embodiment, there is provided a method for producing a lubebase stock and/or a fuel from a feedstock of biological origin, themethod comprising: contacting the feedstock in the presence of acatalyst to produce a lube base stock and/or a fuel, wherein thecatalyst comprises: a zeolite selected from ZSM-48, ZSM-23, ZSM-50,ZSM-5, ZSM-22, ZSM-11, ferrierite, faujasite, beta, ZSM-12, MOR and amixture thereof, and a hydrogenation component comprising at least threemetals selected from the group consisting of Pt, Pd, Ag, Ni, Co, Mo, W,Rh, Re, and Ru, wherein at least one of the at least three metals is ineither an oxide or sulfide form. The catalyst comprising a ternary metalcomponent can be used in a conversion reaction without additional bindercomponent. In an aspect of the present embodiment, the catalyst furthercomprises a hydrothermally stable binder.

Zeolite Component

A zeolite to be employed in the present catalyst composition can beselected based on the intended use of the catalyst. When the catalyst isto be used in isomerization dewaxing, suitable zeolites include thosehaving 10-membered ring pores and particularly those havingunidirectional 10-membered ring pores. Examples of suitable zeolitesinclude ZSM-48, ZSM-23, ZSM-50, ZSM-5, ZSM-22, ZSM-11, ferrierite andcombinations thereof. Other suitable zeolites include those having12-membered ring pores and examples of suitable zeolites include fromfaujasite, beta, ZSM-12, MOR and combinations thereof. Also, suitablezeolites include a combination of a zeolite having 10-membered ringpores and a zeolite having 12-membered ring pores: for example, acombination of beta and ZSM-48.

In particular embodiments, ZSM-48 or ZSM-23 is used as the zeolitecomponent, and the catalysts are particularly useful in theisomerization dewaxing of lube oil basestocks. Such feedstocks arewax-containing feeds that boil in the lubricating oil range, typicallyhaving a 10% distillation point greater than 650° F. (343° C.), measuredby ASTM D86 or ASTM D2887. Such feeds may be derived from a number ofsources such as natural oils like seed oils and animal fats, oilsderived from solvent refining processes such as raffinates, partiallysolvent dewaxed oils, deasphalted oils, distillates, vacuum gas oils,coker gas oils, slack waxes, foots oils and the like, andFischer-Tropsch waxes.

In a particular embodiment, the zeolite component is ZSM-48. ZSM-48crystals, as used herein, is described variously in terms of“as-synthesized” crystals that still contain the organic template;calcined crystals, such as Na-form ZSM-48 crystals; or calcined andion-exchanged crystals, such as H-form ZSM-48 crystals. ZSM-48 crystalsafter removal of the structural directing agent have a particularmorphology and a molar composition according to the general formula:

(n)SiO₂:Al₂O₃

where n is from 70 to 210. In another embodiment, n is 80 to 100. In yetanother particular embodiment, n is 85 to 95. In still otherembodiments, Si may be replaced by Ge and Al may be replaced by Ga, B,Fe, Ti, V, and Zr.

The as-synthesized form of ZSM-48 crystals is prepared from a mixturehaving silica, alumina, base and hexamethonium salt directing agent. Inan embodiment, the molar ratio of structural directing agent:silica inthe mixture is less than 0.05, less than 0.025, or less than 0.022. Inanother embodiment, the molar ratio of structural directing agent:silicain the mixture is at least 0.01, at least 0.015, or at least 0.016. Instill another embodiment, the molar ratio of structural directingagent:silica in the mixture is from 0.015 to 0.025, preferably 0.016 to0.022.

Particularly, the catalysts used in processes according to thedisclosure have a zeolite component with a low ratio of silica toalumina. For example, for ZSM-48, the ratio of silica to alumina in thezeolite can be less than 200:1, less than 110:1, less than 100:1, lessthan 90:1, or less than 80:1. In a particular embodiment, the ratio ofsilica to alumina in the zeolite is less than 80:1, for example,particularly 70:1.

Hydrogenation Component

A hydrogenation component promotes the reaction of hydrogen witholefinic unsaturation in fatty acids, fatty acid dimers and oligomers,ketones, heavier oxygenates, and other intermediate reaction products.It further acts to reduce carbonyl, carboxyl, hydroxyl, and other oxygencontaining groups to provide the saturated hydrocarbons as reactionproducts. Working in concert with other components in the dewaxingcatalysts, it also provides isomerization functionality, helping tointroduce sufficient branching in the final hydrocarbon products, whereneeded, to give basestocks with suitable pour point and low temperatureproperties.

Catalysts suitable for hydrogenation include metals such as Pt, Pd, Ag,Ni, Co, Mo, W, Rh, Re, Ru, Ir as well as binary or ternary mixturesthereof. In various embodiments, the metal hydrogenation component is aGroup VIII noble metal. In non-limiting fashion, the metal hydrogenationcomponent is Pt, Pd or a mixture thereof. In another embodiment, themetal hydrogenation component is a binary mixture, such as, for example,a combination of a non-noble Group VIII metal and a Group VI metal.Suitable combinations include Ni or Co with Mo or W, particularly Niwith Mo or W. In yet another embodiment, the hydrogenation componentcomprises at least three metals selected from the group consisting ofPt, Pd, Ag, Ni, Mo, Co, W, Rh, Re, and Ru, wherein at least one of theat least three metals is in either an oxide or sulfide form. In aparticular embodiment, the metal component is (a) Ni, MoOx and WOx; or(b) Co. MoOx and WOx, wherein x is in the range of 0.5 to 3.

The metal hydrogenation component may be added to the catalyst in anyconvenient manner. One technique for adding the metal hydrogenationcomponent is by incipient wetness. For example, after combining azeolite and a hydrothermally stable binder, the combined zeolite andbinder are extruded into catalyst particles. The catalyst particles areexposed to a solution containing a suitable metal precursor containingthe Group VI or Group VIII metal. Alternatively, metal can be added tothe catalyst by ion exchange, where a metal precursor is added to amixture of zeolite (or zeolite and binder) prior to extrusion. The metalhydrogenation component may be steamed prior to use.

The amount of hydrogenation metal component may range from 0.1 to 5 wt%, based on catalyst. In an embodiment, the amount of metal component isat least 0.1 wt %, at least 0.25 wt %, at least 0.5 wt %, at least 0.6wt %, or at least 0.75 wt %.

Hydrothermally Stable Binders

The catalyst needs to be stable in the presence of water especially whenexcessive water is generated during a conversion reaction. In variousembodiments, a catalyst of the present disclosure comprises a bindercomponent to increase mechanical strength and stability of the catalystin the presence of water under effective hydrogenation conditions. Sucha binder is referred to herein as a “hydrothermally stable binder.”Non-limiting examples of suitable binder components include silica,alumina, silica-alumina, titania, zirconia, tantalum oxide, tungstenoxide, molybdenum oxide, vanadium oxide, magnesium oxide, calcium oxide,yttrium oxide, lanthanum oxide, cerium oxide, niobium oxide, tungstatedzirconia, cobalt molybdenum oxide, cobalt molybdenum sulfide, nickelmolybdenum oxide, nickel molybdenum sulfide, nickel tungsten oxide,nickel tungsten sulfide, cobalt tungsten oxide, cobalt tungsten sulfide,nickel molybdenum tungsten oxide and nickel molybdenum tungsten sulfide,cobalt molybdenum tungsten oxide and cobalt molybdenum tungsten sulfide.

In an embodiment, a hydrothermally stable binder component is selectedfrom binders capable of storing hydrogen, thereby keeping the metal in areduced, highly dispersed state. Non-limiting examples of such bindersinclude tungsten oxide, molybdenum oxide, vanadium oxide, and a mixturethereof.

In another embodiment, a hydrothermally stable binder component is abasic oxide, a binder capable of adsorbing carbon dioxide selectively ora binder which does not change to a denser phase upon exposure to steamand temperatures above 350° C. Non-limiting examples of such bindersinclude magnesium oxide, calcium oxide, yttrium oxide, cerium oxide,niobium oxide, lanthanum oxide, zirconium oxide, and a mixture thereof.

In another embodiment, a hydrothermally stable binder component is acomplex metal oxide used in hydroprocessing. Non-limiting examples ofsuch binders include cobalt molybdenum oxide, cobalt molybdenum sulfide,nickel molybdenum oxide, nickel molybdenum sulfide, nickel tungstenoxide, nickel tungsten sulfide, nickel molybdenum tungsten oxide andnickel molybdenum tungsten sulfide.

In particular embodiments, the hydrothermally stable binder component isselected from lanthanum, cerium, niobium, nickel tungsten oxides, nickeltungsten sulfides, nickel molybdenum tungsten oxides, and nickelmolybdenum tungsten sulfide.

A zeolite can be combined with a binder in any convenient manner. Forexample, a bound catalyst can be produced by starting with powders ofboth the zeolite and binder, combining and mulling the powders withadded water to form a mixture, and then extruding the mixture to producea bound catalyst of a desired size. Extrusion aids can also be used tomodify the extrusion flow properties of the zeolite and binder mixture.

A catalyst comprising a ternary metal hydrogenation component has goodhydrothermal stability with or without a binder. In an embodiment, toachieve improved stability, the catalyst may further comprise a binderselected from various metal oxides. Non-limiting examples of suchbinders include silica, alumina, silica-alumina, titania, zirconia,tantalum oxide, tungsten oxide, molybdenum oxide, vanadium oxide,magnesium oxide, calcium oxide, yttrium oxide, lanthanum oxide, ceriumoxide, niobium oxide, titanium oxide, lanthanum oxide, zirconium oxide,tungstated zirconia, cobalt molybdenum oxide, cobalt molybdenum sulfide,nickel tungsten oxide, nickel tungsten sulfide, nickel molybdenumtungsten oxide, nickel molybdenum tungsten sulfide, and a mixturethereof. In particular embodiments, the hydrothermally stable binder isselected from lanthanum, cerium, niobium, nickel tungsten oxides, nickeltungsten sulfides, nickel molybdenum tungsten oxides, and nickelmolybdenum tungsten sulfide.

Dewaxing Catalysts

A catalyst of this disclosure can be prepared by combining the threecomponents, i.e., a zeolite, a hydrogenation component and a binder.Each of the three components can be selected from various componentsdescribed herein, particularly choosing specific examples listed herein.In various embodiments, for example, the hydrogenation component isselected from Ni and Pt; the zeolite is ZSM-48 or ZSM-23; and thehydrothermally stable binder is selected from nickel molybdenum tungstenoxides, nickel molybdenum tungsten sulfide, WO₃, La₂O₃, CeO₂, and Nb₂O₅.Non-limiting examples of such catalysts include: (a) a catalystcomprising Ni, ZSM-48 and WO₃; (b) a catalyst comprising Ni, ZSM-23 andWO₃; (c) a catalyst comprising Pt, ZSM-48 and La₂O₃; (d) a catalystcomprising Pt, ZSM-48 and CeO₂; (e) a catalyst comprising Pt. ZSM-48 andNb₂O₅; (f) a catalyst comprising Pt, ZSM-23 and La₂O₃; (g) a catalystcomprising Pt, ZSM-23 and CeO₂; (h) a catalyst comprising Pt, ZSM-23 andNb₂O₅; (i) a catalyst comprising Pt, ZSM-48 and WO₃: and (j) a catalystcomprising Pt, ZSM-23 and WO₃, where each of (a) to (j) represents acatalyst comprising three components.

In a particular embodiment, the catalyst comprises 0.6 wt % Ni, ZSM-48and WO₃, wherein the ratio of SiO₂:Al₂O₃ is 80:1 or less, and whereinthe weight ratio of ZSM-48 to WO₃ is 8:2.

In another particular embodiment, the catalyst comprises 3 wt % Ni and20 wt % W, ZSM-48 and alumina, wherein the ratio of SiO₂:Al₂O₃ is 80:1or less, and wherein the weight ratio of ZSM-48 to alumina is 65:35.

In yet another particular embodiment, the catalyst comprises 0.6 wt %Pt, ZSM-48 and Nb₂O₅, wherein the ratio of SiO₂:Al₂O₃ is 80:1 or less,and wherein the weight ratio of ZSM-48 to Nb₂O₅ is 8:2.

In yet another particular embodiment, the catalyst comprises 0.6 wt %Pt, ZSM-48 and La₂O₃, wherein the ratio of SiO₂:Al₂O₃ is 80:1 or less,and wherein the weight ratio of ZSM-48 to La₂O₃ is 8:2.

In yet another particular embodiment, the catalyst comprises 0.6 wt %Pt, ZSM-48 and CeO₂, wherein the ratio of SiO₂:Al₂O₃ is 80:1 or less,and wherein the weight ratio of ZSM-48 to CeO₂ is 8:2.

In yet another particular embodiment, the catalyst comprises 0.6 wt %Pt, CBV-901 and alumina, wherein the weight ratio of ZSM-48 to aluminais 8:2.

In yet another particular embodiment, the catalyst comprises 0.6 wt %Pt, ZSM-48 and TiO₂, wherein the ratio of SiO₂:Al₂O₃ is 90:1 or less,and wherein the weight ratio of ZSM-48 to TiO₂ is 65:35.

In yet another particular embodiment, the catalyst comprises 0.6 wt %Pt, ZSM-23 and alumina, wherein the weight ratio of ZSM-23 to alumina is65:35.

In yet another particular embodiment, the catalyst comprises 0.6 wt %Pt, ZSM-48 and alumina, wherein the ratio of SiO₂:Al₂O₃ is 90 or less,and wherein the weight ratio of ZSM-48 to alumina is 65:35.

When a catalyst comprises a ternary metal component, a zeolite isselected from ZSM-48, ZSM-23, ZSM-50, ZSM-5, ZSM-22, ZSM-11, ferrierite,faujasite, beta, ZSM-12, MOR and a mixture thereof, and a hydrogenationcomponent comprises at least three metals selected from Pt, Pd, Ag, Ni,Co, Mo, W, Rh, Re, and Ru, wherein at least one of the at least threemetals is in either an oxide or sulfide form. In an embodiment, thezeolite is ZSM-48 or ZSM-23; and the hydrogenation component comprises(a) Ni, MoOx and WOx or (b) Co, MoOx and WOx, wherein x is in the rangeof 0.5 to 3.

In a particular embodiment, the catalyst comprises ZSM-48 and ahydrogenation component comprising Ni, MoOx and WOx, where x is in therange of 0.5 to 3, wherein the ratio of SiO₂:Al₂O₃ is 90 or less, andwherein the weight ratio of ZSM-48 to the hydrogenation component is8:2.

Feedstocks

In one embodiment, a process for producing a lube basestock and/or afuel hydrocarbon from a feedstock of biological origin, the methodcomprising: contacting the feedstock in the presence of a catalyst whichcomprises a zeolite component, a hydrogenation component and ahydrothermally stable binder. The feedstock of biological originnormally comprises one or more components selected from the groupconsisting of fatty acids, fatty acid esters, fatty alcohols, fattyolefins, mono-glycerides, di-glycerides, tri-glycerides, phospholipidsand saccharolipids. Optionally water can be co-fed with the biologicalfeedstock, with the water content of 0.5-5 wt % of the total feed.

Feedstocks for the process are drawn from renewable sources ofbiological origin, e.g., plant, algae or animal (including insect)origin. Animal, algae and plant oils containing tri-glycerides, as wellas partially processed oils containing mono-glycerides and di-glyceridesare included in this group. Another source of feedstock is phospholipidsor saccharolipids containing fatty acid esters in their structure, suchas phosphatidyl choline and the like present in plant cell walls. Carbonnumbers for the fatty acid component of such feedstocks are generally inthe range of C₁₂ or greater, up to C₃₀.

Other components of the feed can include a) plant fats, plant oils,plant waxes; animal fats, animal oils, animal waxes; fish fats, fishoils, fish waxes, and mixtures thereof; b) free fatty acids or fattyacids obtained by hydrolysis, acid trans-esterification or pyrolysisreactions from plant fats, plant oils, plant waxes, animal fats, animaloils, animal waxes, fish fats, fish oils, fish waxes, and mixturesthereof; c) esters obtained by trans-esterification from plant fats,plant oils, plant waxes, animal fats, animal oils, animal waxes, fishfats, fish oils, fish waxes, and mixtures thereof, d) esters obtained byesterification of free fatty acids of plant, animal and fish origin withalcohols, and mixtures thereof; e) fatty alcohols obtained as reductionproducts of fatty acids from plant fats, plant oils, plant waxes, animalfats, animal oils, animal waxes, fish fats, fish oils, fish waxes, andmixtures thereof, and f) waste and recycled food grade fats and oils,and fats, oils and waxes obtained by genetic engineering, and mixturesthereof.

Examples of vegetable oils that can be used in accordance with thisdisclosure include, but are not limited to rapeseed (canola) oil,soybean oil, coconut oil, sunflower oil, palm oil, palm kernel oil,peanut oil, linseed oil, tall oil, corn oil, castor oil, jatropha oil,jojoba oil, olive oil, flaxseed oil, camelina oil, safflower oil,babassu oil, tallow oil and rice bran oil. Vegetable oils as referred toherein can also include processed vegetable oil material as a portion ofthe feedstock. Non-limiting examples of processed vegetable oil materialinclude fatty acids and fatty acid alkyl esters. Alkyl esters typicallyinclude C₁-C₅ alkyl esters. One or more of methyl, ethyl, and propylesters are desirable.

Examples of animal fats that can be used in accordance with thedisclosure include, but are not limited to, beef fat (tallow), hog fat(lard), turkey fat, fish fat/oil, and chicken fat. The animal fats canbe obtained from any suitable source including restaurants and meatproduction facilities.

Animal fats as referred to herein also include processed animal fatmaterial. Non-limiting examples of processed animal fat material includefatty acids and fatty acid alkyl esters. Alkyl esters typically includeC₁-C₅ alkyl esters. In particular embodiments, alkyl esters are one ormore of methyl, ethyl, and propyl esters.

Algae oils or lipids can typically be contained in algae in the form ofmembrane components, storage products, and/or metabolites. Certain algalstrains, particularly microalgae such as diatoms and cyanobacteria, cancontain proportionally high levels of lipids. Algal sources for thealgae oils can contain varying amounts, e.g., from 2 wt % to 40 wt % oflipids, based on total weight of the biomass itself.

Algal sources for algae oils can include, but are not limited to,unicellular and multicellular algae. Examples of such algae can includea rhodophyte, chlorophyte, heterokontophyte, tribophyte, glaucophyte,chlorarachniophyte, euglenoid, haptophyte, cryptomonad, dinoflagellum,phytoplankton, and the like, and combinations thereof. In oneembodiment, algae can be of the classes Chlorophyceae and/or Haptophyta.Specific species can include, but are not limited to, Neochlorisoleoabundans, Scenedesmus dimorphus, Euglena gracilis, Phaeodactylumtricornutum, Pleurochrysis carterae, Prymnesium parvum, Tetraselmischui, and Chlamydomonas reinhardtii. Additional or alternate algalsources can include one or more microalgae of the Achnanthes,Amphiprora, Amphora, Ankistrodesmus, Asteromonas, Boekelovia,Borodinella, Botryococcus, Bracteococcus, Chaetoceros, Carteria,Chlamydomonas, Chlorococcum, Chlorogonium, Chlorella, Chroomonas,Chrysosphaera, Cricosphaera, Crypthecodinium, Cryptomonas, Cyclotella,Dunaliella, Ellipsoidon, Emiliania, Eremosphaera, Ernodesmius, Euglena,Franceia, Fragilaria, Gloeothamnion, Haematococcus, Halocafeteria,Hymenomonas, Isochrysis, Lepocinclis, Micractinium, Monoraphidium,Nannochloris, Nannochloropsis, Navicula, Neochloris, Nephrochloris,Nephroselmis, Nitzschia, Ochromonas, Oedogonium, Oocystis, Ostreococcus,Pavlova, Parachlorella, Pascheria, Phaeodactylum, Phagus, Platymonas,Pleurochrysis, Pleurococcus, Prototheca, Pseudochlorella, Pyramimonas,Pyrobotrys, Scenedesmus, Skeletonema, Spyrogyra, Stichococcus,Tetraselmis, Thalassiosira, Viridiella, and Volvox species, and/or oneor more cyanobacteria of the Agmenellum, Anabaena, Anabaenopsis,Anacystis, Aphanizomenon, Arthrospira, Asterocapsa, Borzia, Calothrix,Chamaesiphon, Chlorogloeopsis, Chroococcidiopsis, Chroococcus,Crinalium, Cyanobacterium, Cyanobium, Cyanocystis, Cyanospira,Cyanothece, Cylindrospermopsis, Cylindrospermum, Dactylococcopsis,Dermocarpella, Fischerella, Fremyella, Geitleria, Geitlerinema,Gloeobacter, Gloeocapsa, Gloeothece, Halospirulina, lyengariella,Leptolyngbya, Limnothrir, Lyngbya, Microcoleus, Microcystis,Myxosarcina, Nodularia, Nostoc, Nostochopsis, Oscillatoria, Phormidium,Planktothrix, Pleurocapsa, Prochlorococcus, Prochloron, Prochlorothrix,Pseudanabaena, Rivularia, Schizothrix, Scytonema, Spirulina, Stanieria,Starria, Stigonema, Symploca, Synechococcus, Synechocystis, Tolypothrir,Trichodesmium, Tychonema, and Xenococcus species.

Other feeds usable in the present disclosure can include any of thosethat comprise primarily triglycerides and free fatty acids (FFAs). Thetriglycerides and FFAs typically contain aliphatic hydrocarbon chains intheir structure having from 8 to 36 carbons, particularly from 10 to 26carbons, for example from 14 to 22 carbons. Types of triglycerides canbe determined according to their fatty acid constituents. The fatty acidconstituents can be readily determined using Gas Chromatography (GC)analysis. This analysis involves extracting the fat or oil, saponifying(hydrolyzing) the fat or oil, preparing an alkyl (e.g., methyl) ester ofthe saponified fat or oil, and determining the type of (methyl) esterusing GC analysis. In one embodiment, a majority (i.e., greater than50%) of the triglyceride present in the lipid material is made of C₁₀ toC₂₆ fatty acid constituents, based on total triglyceride present in thelipid material. Further, a triglyceride is a molecule having a structureidentical to the reaction product of glycerol and three fatty acids.Thus, although a triglyceride is described herein as being comprised offatty acids, it should be understood that the fatty acid component doesnot necessarily contain a carboxylic acid hydrogen. If triglycerides arepresent, a majority of triglycerides present in the feed canparticularly be comprised of C₁₂ to C₂₂ fatty acid constituents, basedon total triglyceride content. Other types of feed that are derived frombiological raw material components can include fatty acid esters, suchas fatty acid alkyl esters (e.g., FAME and/or FAEE).

For reactions with feedstocks having a relatively higher degree ofunsaturation, an acidic catalyst can be used to promote dimerization andoligomerization. The dimers and oligomers are branched or having cyclicstructures, so that subsequent hydrogenation under the action of thehydrogenation catalyst produces saturated branched or cyclizedhydrocarbons than can be naturally very low in wax and require little ifany dewaxing. If the feedstock is highly saturated, action of a basiccatalyst produces straight chain products that are subsequentlyhydrogenated to relatively straight chain hydrocarbons that normallyrequire some dewaxing to make them suitable lube stocks. Dewaxing can beprovided by the hydrogenation catalyst, as further described below.

One method for characterizing the triglycerides in a feedstock is basedon the number of carbons in the side chains. While some feedstocks mayhave consistent numbers of carbons in each side chain, such as in atristearin feedstock, many types of triglycerides will have variationsin chain length between molecules and even within molecules. In order tocharacterize these variations, the average number of carbons per sidechain in the triglycerides can be determined. By definition, atriglyceride contains three side chains. Each side chain contains anumber of carbons, as mentioned above. By averaging the number ofcarbons in each side chain for the triglycerides in a feedstock, anaverage side chain length can be determined. The average number ofcarbons (also referred to as average carbon number) per side chain inthe feedstock can be used as a comparative value for characterizingproducts. For example, the average number of carbons per side chain inthe feedstock can be compared with the average number of carbons inhydrocarbons generated by converting and/or isomerizing thetriglyceride-containing feedstock.

In various aspects, the production of fatty acid coupling products andcorresponding hydrogenated products is based on processing oftriglycerides within the feed. Thus, the presence of at least sometriglycerides within the feed is desirable. The feed can include atleast 10 wt % of feed based on a renewable source or sources, such as atleast 25 wt %. In particular embodiments, the renewable portion of thefeed is at least 50 wt %, or at least 75 wt %, or at least 90 wt %, orat least 95 wt %. Such higher amounts of feed from a renewable sourceprovide an advantage based on the greater amount of renewable material.Additionally or alternately, the feed can be entirely a feed from arenewable source, or the feed can include 99 wt % or less of a feedbased on a renewable source, or 90 wt %/o or less, or 75 wt % or less,or 50 wt % or less.

Higher amounts of feed from a renewable source provide an advantagebased on the greater amount of renewable material, as well aspotentially including a greater amount of triglycerides. Feeds withlower amounts of renewable materials may have other processingadvantages. Such advantages can include improved flow characteristicswithin a reaction system, as renewable feeds often have a relativelyhigh viscosity compared to conventional diesel or lubricant feeds in arefinery. Additionally, deoxygenation of a renewable feed can generate asubstantial amount of heat due to formation of highly favorable productsfrom a free energy standpoint, such as H₂O and CO₂. For a typicalcatalyst bed with a bed length of 25 to 30 feet (9 to 10 meters), it maybe preferable to have a temperature increase across the bed of 100° F.(55° C.) or less. If deoxygenation of a renewable feed with high oxygencontent is performed using a sufficiently reactive catalyst, an exothermof greater than 100° F. across the catalyst bed can be generated.Blending a renewable feed with a portion that does not contain oxygencan reduce the exotherm generated across a catalyst bed used forperforming deoxygenation.

Thus the feedstock can contain a number of components. It can besupplied as a solution in a suitable solvent (particularly anon-reactive solvent such as a hydrocarbon), or the feedstock can besupplied neat. The main reactions are thought to be coupling oroligomerizing the fatty acid components (which produces intermediateproducts of suitable carbon number to be useful as diesel fuel and lubebase stocks upon hydrogenation), and hydrogenating the resultingproducts to remove functional groups and produce a saturatedhydrocarbon.

The feed may contain various amount of mineral feed as diluent. Theadvantages of increased mineral feed content are largely due to dilutionof the renewable feed, as the processing conditions effective fordeoxygenation of a renewable feed will have a low or minimal impact on atypical hydroprocessed mineral feed. Therefore, while the deoxygenationconditions are effective for deoxygenation of renewable feeds at avariety of blend ratios with mineral feeds, it may be preferable to haveat least 75 wt % of the feed from a renewable source, such as at least90 wt % or at least 95 wt %.

One option for increasing the renewable content of a feed whileretaining some of the benefits of adding a feed with reduced oxygencontent is to use recycled product from processing of renewable feed asa diluent. A recycled product from processing a renewable feed is stillderived from a renewable source, and therefore such a recycled productis counted as a feed portion from a renewable source. Thus, a feedcontaining 60% renewable feed that has not been processed and 40% of arecycled product from processing of the renewable feed would beconsidered as a feed that includes 100% of feed from a renewable source.As an example, at least a portion of the product from processing of arenewable feed can be a diesel boiling range product. Such a recycleddiesel boiling range product will be deoxygenated, and thereforeincorporation of the recycled diesel boiling range product in the feedwill reduce the exotherm generated during deoxygenation. Adding arecycled diesel boiling range product is also likely to improve the coldflow properties of a renewable feed. More generally, any convenientproduct from processing of a renewable feed can be recycled for blendingwith the renewable feed in order to improve the cold flow propertiesand/or reduce the oxygen content of the input flow to a deoxygenationprocess. If a recycled product flow is added to the input to adeoxygenation process, the amount of recycled product can correspond toat least 10 wt % of the feed to the deoxygenation process, such as atleast 25 wt %, or at least 40 wt %. Additionally or alternately, theamount of recycled product in a feed can be 60 wt % or less, such as 50wt % or less, 40 wt % or less, or 25 wt % or less.

With regard to triglyceride content, the feedstock can include at least10 wt %, such as at least 25 wt %, and particularly at least 40 wt %, orat least 60 wt %, or at least 80 wt %. Additionally or alternately, thefeed can be composed entirely of triglycerides, or the triglyceridecontent of the feed can be 90 wt % or less, such as 75 wt % or less, or50 wt % or less. The methods described herein are suitable forconversion of triglycerides to lubricant and diesel products in a singlereactor, so higher contents of triglycerides may be advantageous.However, to the degree that a recycle loop is used to improve the feedflow properties or reduce the reaction exotherm across catalyst beds,lower triglyceride contents may be beneficial.

While feed dilution can be used to control the exotherm generated acrossa catalyst bed used for deoxygenation, it is noted that some processingoptions can also impact the exotherm. One alternative is to use a lessreactive catalyst, so that a larger amount of catalyst is needed at agiven liquid hourly space velocity (LHSV) in order to deoxygenate a feedto a desired level. Another option is to reduce the amount of hydrogenprovided for the deoxygenation process. Still another option could be tointroduce additional features into a reactor to assist in cooling and/ortransporting heat away from a deoxygenation catalyst bed. In combinationwith selecting an appropriate amount of product recycle and/or blendingof another non-oxygenated feed, a desired combination of a flowcharacteristics and heat generation during deoxygenation can beachieved.

Oxygen is the major heteroatom component in renewable base feeds. Arenewable feedstream based on a vegetable oil, prior to hydrotreatment,includes up to 10 wt % oxygen, for example up to 12 wt % or up to 14 wt%. Such a renewable feedstream, also called a biocomponent feedstream,normally includes at least 1 wt % oxygen, for example at least 2 wt %,at least 3 wt %, at least 4 wt %, at least 5 wt %, at least 6 wt %, orat least 8 wt %. Further, the renewable feedstream, prior tohydrotreatment, can include an olefin content of at least 3 wt %, forexample at least 5 wt % or at least 10 wt %.

Biocomponent based feedstreams have a wide range of nitrogen and/orsulfur contents depending on the feed sources. For example, a feedstreambased on a vegetable oil source can contain up to 300 wppm nitrogen. Insome embodiments, the sulfur content can be 500 wppm or less, forexample 100 wppm or less, 50 wppm or less, or 10 wppm or less, wherewppm stands for parts per million by weight.

Reaction Conditions and Process Configurations

Hydrogen is present throughout the reactor, and is consumed by thereactants during the hydrogenation step. Advantageously, it was foundthat the presence of hydrogen did not adversely affect the fatty acidcoupling reactions believed to be catalyzed primarily by the acidic orbasic catalysts. During the fatty acid coupling, hydrogen transferreactions can lead to formation of coke molecules, which can causecatalyst deactivation. In various embodiments, the presence of hydrogencan inhibit hydrogen transfer and improve catalyst life. In anembodiment, water is added to the renewable feed.

Temperature and pressure of the reactor and reactants is selecteddepending on the throughput and turnover required. Non-limiting examplesof temperatures include 100 to 500° C., 200 to 400° C., and 250 to 400°C. Hydrogen partial pressure is used in the range of from 1.8 to 34.6MPag (250 to 5000 psig) or 4.8 to 20.8 MPag, by way of non-limitingexample. Also in non-limiting fashion, a liquid hourly space velocity isfrom 0.2 to 10 v/v/hr, or 0.5 to 3.0, and a hydrogen circulation rate is35.6 to 1781 m³/m³ (200 to 10,000 scf/B), particularly 178 to 890.6m³/m³ (1,000 to 5000 scf/B). Further non-limiting examples of conditionsare given in working examples.

Loading of the catalyst is 1 to 30% by weight of the weight of thefeedstock in the reactor, for example 2 to 20%, or 5 to 10% by weight.The reaction time or residence time can range from 5 minutes to 50 hoursdepending on types of catalysts used, reaction temperature and theamount (wt %) of catalyst in the reactor. In a particular embodiment, aresidence time is 10 minutes to 10 hours. Shorter residence time givesbetter efficiency for reactor usage. Longer residence time ensures highconversion to pure hydrocarbons. Usually an optimized reactor time ismost desirable.

In various embodiments, the duration of the reaction (or the averageresidence time in the reactor for a continuous process) is 1-48 hours,1-20 hours, 12-36 hours, or 24-30 hours. In various embodiments, thereactions are carried out in a fixed bed reactor, a continuous stir tankreactor, or a batch reactor. In any of these operations, it isadvantageous to maintain partial pressure of hydrogen above 300 psi,above 400 psi, above 500 psi, above 600 psi, or above 700 psi. Duringconversion, carbon dioxide and water generated from the action of theacidic or basic catalyst on the feedstock fatty acids are present ingaseous form, and thus increase the total reactor pressure. Under thiscondition, it can be important to maintain hydrogen partial pressure. Byway of non-limiting example, this can be achieved by intermittentlypurging the reactor gas and re-charging with hydrogen gas in batch orCSTR operation. Alternatively, in a fixed bed operation, this can beachieved by withdrawing reactor gas at different locations along thefixed bed reactor; or alternatively by stage injection of hydrogen.Other means to maintain hydrogen pressure are also possible.

Where needed, the hydrogenation catalyst can introduce branches into thefinal hydrocarbon products to provide a dewaxing function. Fortriglycerides with only saturated fatty acid side chains, thecombination of fatty acid coupling (particularly using a basic materialas the first catalyst) and hydrogenation will be relatively unbranchedhydrocarbons. For triglycerides with both saturated and unsaturatedfatty acid side chains, the combination of fatty acid coupling andhydrogenation will be mixtures of branched hydrocarbons (containing oneor more branches of various lengths in the range of 1 to 10 carbons) andnaphthenics substituted with various lengths of hydrocarbon chains. Ofcourse, if the side chains of the triglycerides contain other types ofheteroatoms, such as nitrogen or sulfur, other types of molecules may begenerated.

For triglycerides with side chains containing between 12 and 22 carbonatoms, the stacked bed configuration of the fatty acid coupling catalystand hydrogenation catalyst will result in production of hydrocarbonmolecules that boil in the lubricant boiling range as a primary product,with some production of hydrocarbon molecules that boil in the dieselboiling range. The lubricant boiling range molecules correspond to fattyacid coupling products that were formed during conversion of thetriglycerides in the feedstock. These fatty acid coupling products aresubsequently hydrogenated and isomerized. However, while the process ofconverting triglycerides will typically occur at percentages approaching100%, less than all of the side chains in the triglycerides may resultin formation of coupling products. Instead, at least a portion of theside chains from the triglycerides will reach the hydrogenation catalystwithout combining with another side chain to form a lubricant boilingrange molecule. These uncombined side chains are also deoxygenated andisomerized by the hydrogenation catalyst, resulting in diesel boilingrange molecules. Thus, a stacked bed arrangement for the catalysts wouldbe expected to generate a majority portion of lubricant boiling rangemolecules from a triglyceride feed and a minority portion of dieselboiling range molecules.

In order to provide a general way of characterizing the hydrocarbonsresulting from conversion, hydrogenation, and isomerization of atriglyceride feed, the average number of carbons (i.e., average carbonnumber) in hydrogenated molecules derived from triglycerides can becompared with the average number of carbons in the fatty acid sidechains of the triglycerides. The average number of carbons inhydrocarbon molecules derived from triglycerides in a feed can be atleast 1.5 times the average number of carbons in the fatty acid sidechains of the corresponding triglycerides, such as at least 1.75 timethe average number of carbons in the fatty acid side chains or at least1.9 times the average number of carbons in the fatty acid side chains.

In a particular embodiment, the average carbon number of hydrocarbonsproduced by conversion of feedstock based triglycerides or other fattyesters is two times or more that of the fatty acid components of thefeedstock. The first catalyst is believed to increase carbon number inthe product by a factor of approximately two or more comparing to thecarbon numbers of the fatty acid side chains in the feed, by the processof coupling (oligomerization, ketonization, and aldol condensation).

Further Processing

The product of the reaction described herein is a mixture ofhydrocarbons, largely saturated, having a carbon number in the dieselfuel and lube base stock range. If desired, the reaction product can behydrofinished by subjecting it to low pressure hydrogen. This processcan clean up residual unsaturations and oxygenates that may result whenthe products are being heated in the presence of the hydrogenationcatalyst, which can have some cracking power given that it may containan acidic carrier such as a zeolite. The hydrofinishing can be carriedout either in a fixed-bed or in an autoclave reactor. The catalyst canbe either noble metal (Pd, Pt, Rh, Ru, Ir, or combination thereof) ornon-noble metal (Co, Ni. Fe), particularly supported on a support suchas clay, alumina, aluminosilicate, silica, titania and zirconia. Theweight hourly space velocity can be in the range of 0.5 to 10 h⁻¹, undera hydrogen pressure in the range of ambient to 30 MPag, and atemperature from 150° C. to 400° C. The resulting product can then befurther processed by distillation to separate out any diesel fuel fromthe lube base stock.

EXAMPLES Example 1 0.6 wt % Pt Impregnated 80/20 Steamed H-ZSM-48/WOx

The title catalyst (0.6 wt % Pt impregnated 80/20 ZSM-48/WOx) wasprepared by the following method: material is first extruded as 80 wt %70:1 SiO₂:Al₂O₃ ZSM-48 and 20 wt % tungsten oxide (designated as WOx).Charge the tungsten oxide to a Lancaster Muller and dry mull for 3minutes. Dilute 28.6 TEAOH (Tetraethylamonium Hydroxide) in 66.1 g ofde-ionized water and slowly add to the WOx. The WOx was mixed by hand ina beaker due to the low volume of material. Wet mull the mixture for 3minutes. Add the ZSM-48 crystal to the peptized WOx and mull 10 minutes.Dilute 57.2 of TEAOH in 627.3 g of deionized water and add to the mullmix over a five minute period. Wet mull the mixture for 20 minutes oruntil the desired consistency is achieved. Extrude the mull mixture on a2″ Bonnot extruder using 1/16″ quadrulobe die inserts.

Pre-calcine the bound zeolite in flowing N₂ at 950° F. (510° C.) forthree hours to start removing the structure directing agent from thezeolite. Ammonium-exchange the formed material two times (5 ml of 1 MNH₄NO₃ solution per gram of catalyst) under ambient conditions to removethe alkali cations from the structure. After completing the secondexchange wash the material with de-ionized water for one hour. Dry at250° F. (121° C.) overnight in a forced draft oven. To create the acidform of the catalyst, calcine the extrudate in air for 6 hours at 1,000°F. (538° C.) in air.

Place the acid form of the catalyst into a vertical steamer. Bringcatalyst up to 650° F. (343° C.) in air and hold at temperature for 30minutes. Switch from air to steam over a 30-minute period. Ramp thetemperature of the steamer to 700° F. (371° C.), allow the temperaturein the bed to stabilize, and hold for 3 hours at 700° F. in 100% steam.Cool down in air and remove the catalyst from the steamer.

Impregnate the steamed acid form of the catalyst using a tetraamineplatinum nitrate solution via spray impregnation targeting a metalloading of 0.6 wt % Pt. Spray in the impregnating solution slowly; afterthe solution has been applied continue mixing for 20 minutes to insurethat the solution is uniformly distributed across all of the extrudates.Dry at ambient conditions in an open dish. Dry for 2 hours in a forcedair oven at 250° F. Complete the impregnation by calcining the extrudatein air at 680° F. (360° C.) for three hours.

The finished catalyst had 0.56 wt % Pt on catalyst. Dispersion of Pt wasmeasure by H₂ chemisorption, a H/Pt molar ratio of 4.02 was observed,indicating high degree of Pt dispersion (equivalent to smaller Ptparticles on catalyst).

Example 2 80/20 H-ZSM-48/NiMoWOx

The title catalyst (80/20 H-ZSM-48/NiMoWOx) was prepared by thefollowing method: charge the NiMoWOx to a Lancaster Muller and dry mullfor 3 hours. Dilute 28.6 g of 35 wt % TEAOH in 66.1 g of de-ionizedwater. Slowly add the solution to the NiMoWOx. Wet mull the mixture for3 minutes. Add the ZSM-48 crystal to the peptized NiMoWOx and mull 10minutes. Dilute 57.2 g of 35 wt % TEAOH in 680.2 g of de-ionized water.Add the solution to the mull mix over a five minute period. Wet mull for20 minutes or until reasonable consistency is achieved. Extrude the mullmix on a 2″ Bonnot extruder equipped with a die plate using 1/16″quadrulobe die inserts. Dry in a forced air oven at 250° F. to dry theextrudate.

Pre-calcine the extrudate in flowing nitrogen at 950° F. for 3 hours.Ammonium-exchange the extrudate two times under ambient conditions (5 mlof 1 N NH₄NO₃ solution per gram of catalyst). After the completion oftwo exchanges, wash with DI water for 1 hour at room temperature, drain,and dry under ambient conditions. Dry at 250° F. overnight in a forceddraft oven. Heat the extrudate under nitrogen to 752° F. (300° C.) forthree hours. Lower the temperature of the oven to 700° F. and beginintroducing air over a three hour period. The final air calcinationshould be completed at 1,000° F. under air for 10 hours.

Loadings of metal on the finished catalyst were 3.45 wt % W, 2.41 wt %Ni, and 1.92 wt % Mo.

Example 3 3 wt % Ni and 20 wt % W Impregnated 65/35 ZSM-48/Alumina(V-300)

The title catalyst (3 wt % Ni and 20 wt % W impregnated 65/35ZSM-48/V-300) was prepared by the following method: charge 1,639 g ofZSM-48 (SiO₂:Al₂O₃=70:1) crystal to the muller and mull for 10 minutes.Add 1153 g of Versal-300 alumina to the muller and mull for 10 minutes.Slowly add 1547 g of de-ionized water to mull mix while mulling. Mullthe mixture for 40 minutes or until a reasonable mixture consistency isachieved. Extrude the mixture on the 2″ Bonnot extruder using a dieplate with 1/20″ quadrulobe inserts. After extrusion, dry at 250° F. ina forced draft oven.

Pre-calcine the extrudate prepared above for 3 hours at 1,000° F. inflowing nitrogen. After calcining the extrudate under inert conditions,exchange the material two times with ammonium nitrate (5 ml of 1 NNH₄NO₃ solution per gram of catalyst). After the second exchange washthe material with de-ionized water for 1 hour at room temperature,drain, and blow dry with air. Dry the exchanged material in a forceddraft oven at 250° F. overnight. Calcine the ammonium form of theextrudate for 6 hours at 1,000° F. in air to create the acid form of thecatalyst.

Impregnate the extrudate with 20 wt % W using ammonium metatungstatehydrate using a rotary spray impregnation technique. For example, 500 gof extrudate would be impregnated with 134 g of ammonium metatungstatehydrate dissolved in water. After the material is sprayed onto thecatalyst the catalyst should be mixed for an additional 30 minutes toimprove the homogeneity of the metal dispersion. Dry the extrudate for 4hours at ambient conditions in a pan. Dry the catalyst overnight in aforced draft oven at 250° F. Calcine the extrudates in air at 900° F.for 1 hour.

The resulting catalyst had 14 wt % tungsten and 3 wt % Ni as measured byXRF analysis.

Example 4 0.6 wt % Ni Impregnated 80/20 Steamed H-ZSM-48/WOx

The title catalyst (0.6 wt % Ni impregnated 80/20 ZSM-48/WOx) wasprepared by the following method: the 80:20 ratio of ZSM-48 and WOxextrudate formed in Example 1 is impregnated with 0.6 wt % Ni instead of0.6 wt % Pt. Impregnate the steamed acid form of the catalyst using anickel nitrate hexahydrate solution via spray impregnation targeting ametal loading of 0.6 wt % Ni. Spray in the impregnating solution slowly;after the solution has been applied continue mixing for 30 minutes toinsure that the solution is uniformly distributed across all of theextrudates. Dry the extrudate for 4 hours at ambient conditions in apan. Dry the catalyst overnight in a forced draft oven at 250° F.Calcine the extrudates in air at 900° F. for 3 hours. The finishedcatalyst contained 0.69 wt % Ni.

Example 5 0.6 wt % Pt Impregnated 80/20 Steamed H-ZSM-48/Niobium Oxide

The title catalyst (0.6 wt % Pt impregnated 80/20 ZSM-48/niobium oxide)was prepared by the following method: material is first extruded as 80wt % 70:1 SiO₂:Al₂O₃ ZSM-48 and 20 wt % niobium oxide. Charge theniobium oxide to a Lancaster Muller and dry mull for 3 minutes. Dilute17.1 g of 35 wt %/o TEAOH in 39.7 g of de-ionized water and slowly addto the niobium oxide. Wet mull the mixture for 3 minutes. Add the ZSM-48crystal to the peptized niobium oxide and mull for 10 minutes. Dilute34.3 g of 35 wt % TEAOH in 356.2 g of deionized water and add to themull mix over a five minute period. Wet mull the mixture for 20 minutesor until the desired consistency is achieved. Extrude the mull mixtureon a 2″ Bonnot extruder using 1/16″ quadrulobe die inserts.

Pre-calcine the bound zeolite in flowing N₂ at 950° F. for three hoursto start removing the structure directing agent from the zeolite.Ammonium-exchange the formed material two times (5 ml of 1 M NH₄NO₃solution per gram of catalyst) under ambient conditions to remove thealkali cations from the structure. After completing the second exchangewash the material with de-ionized water for one hour. Dry at 250° F.overnight in a forced draft oven. To create the acid form of thecatalyst, calcine the extrudate in air for 6 hours at 1,000° F. in air.

Place the acid form of the catalyst into a vertical steamer. Bringcatalyst up to 650° F. in air and hold at temperature for 30 minutes.Switch from air to steam over a 30-minute period. Ramp the temperatureof the steamer to 700° F., allow the temperature in the bed tostabilize, and hold for 3 hours at 700° F. in 100% steam. Cool down inair and remove the catalyst from the steamer.

Impregnate the steamed acid form of the catalyst using a tetraamineplatinum nitrate solution via spray impregnation targeting a metalloading of 0.6 wt % Pt. Spray in the impregnating solution slowly; afterthe solution has been applied continue mixing for 20 minutes to insurethat the solution is uniformly distributed across all of the extrudates.Dry at ambient condition in an open dish. Dry for 2 hours in a forcedair oven at 250° F. Complete the impregnation by calcining the extrudatein air at 680° F. for three hours.

H₂ chemisorption revealed a Pt dispersion of H/Pt=0.73.

Example 6 0.6 wt % Pt Impregnated 80/20 Steamed H-ZSM-48/La₂O₃

The title catalyst (0.6 wt % Pt impregnated 80/20 ZSM-48/La₂O₃) wasprepared by the following method: the material is first extruded as 80wt % 70:1 SiO₂:Al₂O₃ ZSM-48 and 20 wt % lanthanum oxide. Charge 125 g oflanthanum oxide to a Lancaster Muller and dry mull for 3 minutes. Dilute17.1 g of 35 wt % TEAOH in 29.7 g of de-ionized water and slowly add thesolution to the lanthanum oxide. Wet mull the mixture for 3 minutes. Addthe ZSM-48 crystal to the peptized lanthanum oxide and mull 10 minutes.Dilute 34.3 g of 35 wt % TEAOH in 356.2 g of deionized water and add tothe mull mix over a five-minute period. Wet mull the mixture for 20minutes or until the desired consistency is achieved. Extrude the mullmixture on a 2″ Bonnot extruder using 1/16″ quadrulobe die inserts.

Pre-calcine the bound zeolite in flowing N₂ at 950° F. for three hoursto start removing the structure directing agent from the zeolite.Ammonium-exchange the formed material two times (5 ml of 1 M NH₄NO₃solution per gram of catalyst) under ambient conditions to remove thealkali cations from the structure. After completing the second exchangewash the material with de-ionized water for one hour. Dry at 250° F.overnight in a forced draft oven. To create the acid form of thecatalyst, calcine the extrudate in air for 6 hours at 1,000° F. in air.

Place the acid form of the catalyst into a vertical steamer. Bringcatalyst up to 650° F. in air and hold at temperature for 30 minutes.Switch from air to steam over a 30-minute period. Ramp the temperatureof the steamer to 700° F., allow the temperature in the bed tostabilize, and hold for 3 hours at 700° F. in 100% steam. Cool down inair and remove the catalyst from the steamer.

Impregnate the steamed acid form of the catalyst using a tetraamineplatinum nitrate solution via spray impregnation targeting a metalloading of 0.6 wt % Pt. Spray in the impregnating solution slowly; afterthe solution has been applied continue mixing for 20 minutes to insurethat the solution is uniformly distributed across all of the extrudates.Dry at ambient conditions in an open dish. Dry for 2 hours in a forcedair oven at 250° F. Complete the impregnation by calcining the extrudatein air at 680° F. for three hours.

The finished catalyst had 0.56 wt % Pt on catalyst. H₂ chemisorptionrevealed a Pt dispersion of H/Pt=1.18.

Example 7 0.6 wt % Pt Impregnated 80/20 Steamed H-ZSM-48/CeO₂

The title catalyst (0.6 wt % Pt impregnated 80/20 ZSM-48/CeO₃) wasprepared by the following method: the material is first extruded as 80wt % 70:1 SiO₂:Al₂O₃ ZSM-48 and 20 wt % cerium oxide. Charge 122 g ofcerium oxide to a Lancaster Muller and dry mull for 3 minutes. Dilute17.1 g of 35 wt % TEAOH in 39.7 g of de-ionized water and slowly add thesolution to the cerium oxide. Wet mull the mixture for 3 minutes. Addthe ZSM-48 crystal to the peptized lanthanum oxide and mull 10 minutes.Dilute 34.3 g of 35 wt % TEAOH in 419.7 g of deionized water and add tothe mull mix over a five-minute period. Wet mull the mixture for 20minutes or until the desired consistency is achieved. Extrude the mullmixture on a 2″ Bonnot extruder using 1/16″ quadrulobe die inserts.

Pre-calcine the bound zeolite in flowing N₂ at 950° F. for three hoursto start removing the structure directing agent from the zeolite.Ammonium-exchange the formed material two times (5 ml of 1 M NH₄NO₃solution per gram of catalyst) under ambient conditions to remove thealkali cations from the structure. After completing the second exchangewash the material with de-ionized water for one hour. Dry at 250° F.overnight in a forced draft oven. To create the acid form of thecatalyst, calcine the extrudate in air for 6 hours at 1,000° F. in air.

Place the acid form of the catalyst into a vertical steamer. Bringcatalyst up to 650° F. in air and hold at temperature for 30 minutes.Switch from air to steam over a 30-minute period. Ramp the temperatureof the steamer to 700° F., allow the temperature in the bed tostabilize, and hold for 3 hours at 700° F. in 100% steam. Cool down inair and remove the catalyst from the steamer.

Impregnate the steamed acid form of the catalyst using a tetraamineplatinum nitrate solution via spray impregnation targeting a metalloading of 0.6 wt % Pt. Spray in the impregnating solution slowly; afterthe solution has been applied continue mixing for 20 minutes to insurethat the solution is uniformly distributed across all of the extrudates.Dry at ambient conditions in an open dish. Dry for 2 hours in a forcedair oven at 250° F. Complete the impregnation by calcining the extrudatein air at 680° F. for three hours.

The finished catalyst had 0.42 wt % Pt on catalyst. H₂ chemisorptionrevealed a Pt dispersion of H/Pt=0.78.

Example 8 0.6 wt % Pt Impregnated 80/20 CBV-901/Alumina

The title catalyst (0.6 wt % Pt impregnated 80/20 CBV-901/alumina) wasprepared by the following method: The material is first extruded as a 80wt % CBV-901 and 20 wt % Versal 300 alumina composite using thefollowing procedure. Charge 808 g of CBV-901 USY crystal to a LancasterMuller and dry mull for 5 minutes. Dilute 10 g of acetic acid with 690 gof de-ionized water. Dissolve 5 g of polyvinylacetate (PVA) in theacetic acid solution. Slowly add the acid/PVA solution to the zeoliteover 5 minutes and mull the mixture for 10 minutes. Add 275 g ofVersal-300 alumina to the muller and mull for an additional 10 minutes.Add the remaining 173 g of de-ionized water to the mull mix over 3minutes and mull 3 minutes or until reasonable consistency is achieved.Extrude the mull mixture on a 2″ Bonnot extruder using 1/16″ quadrulobedie inserts. Dry the extrudates at 250° F. Calcine the dried extrudatesin air at 1,000° F. for 6 hours.

Impregnate the acid form of the catalyst using a tetraamine platinumnitrate solution via spray impregnation targeting a metal loading of 0.6wt % Pt. Spray in the impregnating solution slowly; after the solutionhas been applied continue mixing for 20 minutes to insure that thesolution is uniformly distributed across all of the extrudates. Dry atambient conditions in an open dish. Dry for 2 hours in a forced air ovenat 250° F. Complete the impregnation by calcining the extrudate in airat 680° F. for three hours.

Example 9 0.6 wt % Pt Impregnated 65/35 Steamed H-ZSM-48/TiO₂

The title catalyst (0.6 wt % Pt impregnated 65/35 ZSM-48/TiO₂) wasprepared by the following method: the material is first extruded as 65wt % 90:1 SiO₂:Al₂O₃ ZSM-48 and 35 wt % titanium oxide. Charge theZSM-48 to the muller and mull for 10 minutes. Add 214 g of DT-51 titaniato muller and mull for 10 minutes. Slowly add 488 g of de-ionized waterto mull mix while mulling. Mull the mixture for 30 minutes or until themixture reaches the desired consistency to extrude properly. Extrudemixture on a 2″ Bonnot extruder equipped with a die plate using 1/16″quadrulobe inserts. Dry the extrudate at 250° F. in a forced draft oven.

Pre-calcine the bound zeolite in flowing N₂ at 1,000° F. for 3 hours tostart removing the structure directing agent from the zeolite.Ammonium-exchange the formed material two times (5 ml of 1 M NH₄NO₃solution per gram of catalyst) under ambient conditions to remove thealkali cations from the structure. After completing the second exchangewash the material with de-ionized water for one hour. Dry at 250° F.overnight in a forced draft oven. To create the acid form of thecatalyst, calcine the extrudate in air for 6 hours at 1,000° F. in air.

Place the acid form of the catalyst into a vertical steamer. Bringcatalyst up to 700° F. in air and hold at temperature for 30 minutes.Switch from air to steam over a 30-minute period. Ramp the temperatureof the steamer to 890° F., allow the temperature in the bed tostabilize, and hold for 3 hours at 890° F. in 100% steam. Cool down inair and remove the catalyst from the steamer.

Impregnate the steamed acid form of the catalyst using a tetraamineplatinum nitrate solution via spray impregnation targeting a metalloading of 0.6 wt % Pt. Spray in the impregnating solution slowly; afterthe solution has been applied continue mixing for 20 minutes to insurethat the solution is uniformly distributed across all of the extrudates.Dry at ambient conditions in an open dish. Dry for 2 hours in a forcedair oven at 250° F. Complete the impregnation by calcining the extrudatein air at 680° F. for 3 hours.

H₂ chemisorption revealed a Pt dispersion of H/Pt=0.76.

Example 10 0.6 wt % Pt Impregnated 65/35 H-ZSM-23/Alumina

The title catalyst (0.6 wt % Pt impregnated 65/35 ZSM-23/alumina) wasprepared by the following method: the material is first extruded as 65wt % ZSM-23 and 35 wt % Versal 300 alumina. Charge the 433 g of ZSM-23crystal to muller and dry mull for 15 minutes. Add the 248 g of Versal300 alumina to the muller and dry mull for an additional 10 minutes.Slowly add 451.3 g of de-ionized water to the mull mix over 5 minutesand mull the mixture for 10 minutes or until reasonable consistency.Extrude the mixture on a 2″ Bonnot extruder equipped with a die plateusing 1/16″ quadrulobe inserts. Dry the extrudate at 250° F. in a forceddraft oven.

Pre-calcine the bound zeolite in flowing N₂ at 1,000° F. for 3 hours tostart removing the structure directing agent from the zeolite.Ammonium-exchange the formed material two times (5 ml of 1 M NH₄NO₃solution per gram of catalyst) under ambient conditions to remove thealkali cations from the structure. After completing the second exchangewash the material with de-ionized water for one hour. Dry at 250° F.overnight in a forced draft oven. To create the acid form of thecatalyst, calcine the extrudate in air for 8 hours at 1,000° F. in air.

Impregnate the acid form of the catalyst using a tetraamine platinumnitrate solution via spray impregnation targeting a metal loading of 0.6wt % Pt. Spray in the impregnating solution slowly; after the solutionhas been applied continue mixing for 20 minutes to insure that thesolution is uniformly distributed across all of the extrudates. Dry atambient conditions in an open dish. Dry for 2 hours in a forced air ovenat 250° F. Complete the impregnation by calcining the extrudate in airat 680° F. for 3 hours.

The finished catalyst had 0.52 wt % Pt on catalyst. H₂ chemisorptionrevealed a Pt dispersion of H/Pt=1.25.

Example 11 0.6 wt % Pt Impregnated 65/35 H-ZSM-48/Alumina

The title catalyst (0.6 wt % Pt impregnated 65/35 ZSM-48/alumina) wasprepared by the following method: add 245 lbs. of ZSM-48 SiO₂/Al₂O₃ 90to the muller. Mull the mixture for ten minutes. Add 162 lbs. of Versal300 alumina. Mull the mixture for ten minutes after adding all of thealumina. Add 292 lbs. of de-ionized water while mulling. Mull themixture for forty minutes or until reasonable consistency is achieved.Extrude the mixture on an extruder equipped with a die plate using 1/16″quadrulobe inserts. Dry the extrudate at 250° F. in a forced draft oven.

Pre-calcine the bound zeolite in flowing N₂ at 980° F. for 3 hours tostart removing the structure directing agent from the zeolite.Ammonium-exchange the formed material two times (5 ml of 1 M NH₄NO₃solution per gram of catalyst) under ambient conditions to remove thealkali cations from the structure. After completing the second exchangewash the material with de-ionized water for one hour. Dry at 250° F.overnight in a forced draft oven. To create the acid form of thecatalyst, calcine the extrudate in air for 6 hours at 980° F. in air.

Place the acid form of the catalyst into a vertical steamer. Bringcatalyst up to 650° F. in air and hold at temperature for 30 minutes.Switch from air to steam over a 30-minute period. Ramp the temperatureof the steamer to 890° F., allow the temperature in the bed tostabilize, and hold for 3 hours at 890° F. in 100% steam. Cool down inair and remove the catalyst from the steamer.

Impregnate the steamed acid form of the catalyst using a tetraamineplatinum nitrate solution via spray impregnation targeting a metalloading of 0.6 wt % Pt. Spray in the impregnating solution slowly; afterthe solution has been applied continue mixing for 20 minutes to insurethat the solution is uniformly distributed across all of the extrudates.Dry at ambient conditions in an open dish. Dry for 2 hours in a forcedair oven at 250° F. Complete the impregnation by calcining the extrudatein air at 680° F. for three hours.

Example 12 Steaming of the 0.6 wt % Pt Impregnated 65/35 ZSM-48/TiO₂

Place the Pt form of the catalyst from Example 8 into a verticalsteamer. Bring catalyst up to 950° F. in air and hold at temperature for30 minutes. Switch from air to steam over a 30 minute period. Ramp thetemperature of the steamer to 1,000° F., allow the temperature in thebed to stabilize, and hold for 24 hours at 1,000° F. in 100% steam. Cooldown in air and remove the catalyst from the steamer.

Example 13 Steaming of the 0.6 wt % Pt Impregnated 65/35 ZSM-23/Alumina

Place the Pt form of the catalyst from Example 10 into a verticalsteamer. Bring catalyst up to 950° F. in air and hold at temperature for30 minutes. Switch from air to steam over a 30 minute period. Ramp thetemperature of the steamer to 1,000° F., allow the temperature in thebed to stabilize, and hold for 24 hours at 1,000° F. in 100% steam. Cooldown in air and remove the catalyst from the steamer.

Catalyst candidates were first screened through a “severe steamingprocess” which consisted of steaming each potential lead at 1,000° F.for 24 hours in order to examine the effects that exposure to water athigh temperatures would have on the crush strength and metal dispersionof each material. Pt dispersions were measured by H₂ chemisorption. Apromising lead candidate for this application would maintain its crushstrength with minimal metal agglomeration. Catalyst from Example 11 wasincluded in the study as a point of reference. The results of the severesteaming study are shown in Table 1.

TABLE 1 Summary of Steaming Study Results Crush Strength Crush Strengthbefore steaming after steaming H/Pt before H/Pt after Example (lb/in)(lb/in) steaming steaming 1 18.06 25.33 0.49 0.43 8 152.31 129.38 1.370.172 9 30.69 25.75 0.76 0.2 10 79.01 78.52 1.26 0.407 11 156.05 132.351.31 0.195

It can be seen that the catalyst of Example 1 maintained metaldispersion (indicted by H/Pt) and showed slightly higher crush strengthafter severe steaming.

Example 14 Catalytic Testing for Dewaxing of Oxygenated Feeds

Catalytic testing was conducted on a High Pressure Heated Orbital Shakerhigh-throughput experimentation device, which is a collection of smallbatch reactors contained in a heated, high pressure enclosure.Individual batch reactors consist of a 40 mm deep well with an internalvolume of 5.15 cm³ each. Each individual well was charged with acatalyst along with 18-pentatriacontanone feed and run at 800 psig H₂,350° C., and WHSV of 1 to 2 hr⁻¹ over a course of 24 hours. Withoutbeing bound to any theory or structural details, the reaction isschematically represented below. The results are shown in Table 2.

TABLE 2 Catalytic testing results Total Pendant Con- Epsilon PendantMethyl # Side Free Ex- version Carbon, Groups, Groups, Chains/ CarbonCarbon ample (%) mole % mole % mole % Molecule # Index  1  91 22.03 9.44  7.17 1.87 26.08 5.75  2  98 10.23 10.94  8.24 2.44 29.57 3.03  3 91 22.55  7.95  5.72 1.52 26.47 5.97  5  99 10.19 13.35  9.70 2.2823.54 2.40  6 100 22.07 10.04  7.86 2.33 29.64 6.54  7 100 12.13 12.76 9.43 2.28 24.16 2.93  9 100  8.41 13.15 10.08 2.96 29.40 2.47 11 100 4.75 14.22 10.41 2.68 25.78 1.22

Under the conditions tested, all catalysts disclosed herein effectivelydewaxed the ketone feed (conversions of ketone >90%) giving liquidproducts.

The products were characterized using quantitative ¹³C NMR. Quantitative¹³C NMR spectra were obtained using Cr(acac)3 as a relaxation aid duringacquisition. For example, all normal paraffins with carbon numbersgreater than C₉ have only five inequivalent carbon NMR absorptions,corresponding to the terminal methyl carbons (α), methylene carbons atthe second, third, and fourth positions from the molecular ends (β, γand δ, respectively), and the other carbon atoms along the backbone thathave a common shift (ε). The intensities of α, β, γ and δ are equal andthe intensity of ε carbons depends on the length of the molecule.Similarly, side branches on the backbone of an iso-paraffin have uniquechemical shifts and the presence of side-chain causes a unique shift atthe tertiary site on the backbone to which it is anchored. It alsoperturbs the chemical shifts within three sites of the tertiary site,imparting unique chemical shifts (α′, β′ and γ′) to the adjacent siteswhen they occur in the center of a long backbone. The number of freeends of molecules can be estimated by measuring the number of α, β, γand δ carbons. Unique shifts also enable measuring the number of pendantside-chains of different length (which are called P-Me, P-Et, P-Pr, andP-Bu). The molecular ends that have a side branch at the 2, 3, 4, or 5sites (which are called T-Me, T-Et, T-Pr and T-Bu) can also be measured.The branching features are particularly valuable in characterizing lubebasestocks.

The products can be characterized by the “Free Carbon Index”, whichrepresents the measure of carbon atoms in an average molecule that areepsilon carbons:

FCI=(% epsilon carbons)×(Carbon Number)/100,

where the Carbon Number is determined by ¹³C NMR as following:

Carbon Number=2/((mole % α carbon+mole % T-Me carbon+mole % T-Etcarbon+mole % T-Pr carbon)/100)

¹³C NMR also revealed that the products are significantly free ofcarbonyl carbon, consistent with high conversions seen by GC. Thedewaxed products had, on average, 1-3 side chain per molecule,indicating effective dewaxing of the ketone feed.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the disclosure have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe disclosure. Accordingly, it is not intended that the disclosure belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including” for purposes of Australian law.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.

While the illustrative embodiments of the disclosure have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of thedisclosure. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present disclosure,including all features which would be treated as equivalents thereof bythose skilled in the art to which the disclosure pertains.

What is claimed is:
 1. A method for producing a lube base stock and/or afuel from a feedstock of biological origin, the method comprising:contacting the feedstock in the presence of a catalyst to produce a lubebase stock and/or a fuel, wherein the catalyst comprises: a zeolitecomponent selected from a zeolite having 10-member ring pores, a zeolitehaving 12-member ring pores and a combination thereof, 0.1 to 5 weight %of a hydrogenation component selected from Pt, Pd, Ag, Ni, Mo, Co, W,Rh, Re, Ru, Ir and a mixture thereof, and a hydrothermally stable bindercomponent selected from silica, alumina, silica-alumina, titania,zirconia, tantalum oxide, tungsten oxide, molybdenum oxide, vanadiumoxide, magnesium oxide, calcium oxide, yttrium oxide, lanthanum oxide,cerium oxide, niobium oxide, tungstated zirconia, cobalt molybdenumoxide, cobalt molybdenum sulfide, nickel molybdenum oxide, nickelmolybdenum sulfide, nickel tungsten oxide, nickel tungsten sulfide,cobalt tungsten oxide, cobalt tungsten sulfide, nickel molybdenumtungsten oxide and nickel molybdenum tungsten sulfide, cobalt molybdenumtungsten oxide and cobalt molybdenum tungsten sulfide, wherein theweight ratio of the zeolite component to the hydrothermally stablebinder component is 85:15 to 25:75.
 2. The method of claim 1, whereinthe method produces jet fuel, diesel fuel, or gasoline.
 3. The method ofclaim 1, wherein the method produces lube base stock.
 4. The method ofclaim 1, wherein the feedstock of biological origin comprises one ormore components selected from the group consisting of fatty acids, fattyacid esters, fatty alcohols, fatty olefins, mono-glycerides,di-glycerides, tri-glycerides, phospholipids and saccharolipids.
 5. Themethod of claim 1, further comprising providing hydrogen.
 6. The methodof claim 1, further comprising adding water to the feedstock ofbiological origin.
 7. The method of claim 1, wherein the weight ratio ofthe zeolite component to the hydrothermally stable binder component is80:20 to 65:35.
 8. The method of claim 1, wherein the hydrogenationcomponent is selected from Pt, Pd, Ni, Mo, W and a binary mixturethereof.
 9. The method of claim 1, wherein the zeolite component isselected from ZSM-48, ZSM-23, ZSM-50, ZSM-5, ZSM-22, ZSM-11, ferrierite,faujasite, beta, ZSM-12, MOR and a combination thereof.
 10. The methodof claim 1, wherein the zeolite component is a combination of beta andZSM-48.
 11. The method of claim 1, wherein the zeolite component isZSM-48 or ZSM-23, wherein the ratio of SiO₂:Al₂O₃ is 100 or less. 12.The method of claim 1, wherein the hydrothermally stable bindercomponent is selected from tungsten oxide, molybdenum oxide, vanadiumoxide, and a mixture thereof
 13. The method of claim 1, wherein thehydrothermally stable binder component is selected from magnesium oxide,calcium oxide, yttrium oxide, cerium oxide, niobium oxide, lanthanumoxide, zirconium oxide, and a mixture thereof.
 14. The method of claim1, wherein the hydrothermally stable binder component is selected fromcobalt molybdenum oxide, cobalt molybdenum sulfide, nickel molybdenumoxide, nickel molybdenum sulfide, nickel tungsten oxide, nickel tungstensulfide, nickel molybdenum tungsten oxide and nickel molybdenum tungstensulfide.
 15. The method of claim 1, wherein the hydrothermally stablebinder component is lanthanum, cerium, niobium, nickel tungsten oxides,nickel tungsten sulfides, nickel molybdenum tungsten oxides, and nickelmolybdenum tungsten sulfide.
 16. The method of claim 1, wherein thehydrogenation component is Ni or Pt; the zeolite component is ZSM-48 orZSM-23; and the hydrothermally stable binder component is nickelmolybdenum tungsten oxides, nickel molybdenum tungsten sulfide, WO₃,La₂O₃, CeO₂, or Nb₂O₅.
 17. The method of claim 1, wherein the catalystcomprises a mixture selected from: (a) Ni, ZSM-48 and WO₃; (b) Ni,ZSM-23 and WO₃ (c) Pt, ZSM-48 and La₂O₃; (b) Pt, ZSM-48 and CeO₂; (e)Pt, ZSM-48 and Nb₂O₅; (f) Pt, ZSM-23 and La₂O₃; (c) Pt, ZSM-23 and CeO₂;(h) Pt, ZSM-23 and Nb₂O₅; (d) Pt, ZSM-48 and WO₃; and (j) Pt, ZSM-23 andWO₃.
 18. The method of claim 1, wherein the catalyst is selected from:(i) a catalyst comprising 0.6 weight % Ni, ZSM-48 and WO₃, wherein theratio of SiO₂:Al₂O₃ is 80:1 or less, and wherein the weight ratio ofZSM-48 to WO₃ is 8:2; (ii) a catalyst comprising 3 weight % Ni and 20%W, ZSM-48 and alumina, wherein the ratio of SiO₂:Al₂O₃ is 80:1 or less,and wherein the weight ratio of ZSM-48 to alumina is 65:35; (iii) acatalyst comprising 0.6 weight % Pt, ZSM-48 and Nb₂O₅, wherein the ratioof SiO₂:Al₂O₃ is 80:1 or less, and wherein the weight ratio of ZSM-48 toNb₂O₅ is 8:2; (iv) a catalyst comprising 0.6 weight % Pt, ZSM-48 andLa₂O₃, wherein the ratio of SiO₂:Al₂O₃ is 80:1 or less, and wherein theweight ratio of ZSM-48 to La₂O₃ is 8:2; (v) a catalyst comprising 0.6weight % Pt, ZSM-48 and CeO₂, wherein the ratio of SiO₂:Al₂O₃ is 80:1 orless, and wherein the weight ratio of ZSM-48 to CeO₂ is 8:2; (vi) acatalyst comprising 0.6 weight % Pt, CBV-901 and alumina, wherein theweight ratio of ZSM-48 to alumina is 8:2; (vii) a catalyst comprising0.6 weight % Pt, ZSM-48 and TiO₂, wherein the ratio of SiO₂:Al₂O₃ is90:1 or less, and wherein the weight ratio of ZSM-48 to TiO₂ is 65:35;(viii) a catalyst comprising 0.6 weight % Pt, ZSM-23 and alumina,wherein the weight ratio of ZSM-23 to alumina is 65:35; and (ix) acatalyst comprising 0.6 weight % Pt, ZSM-48 and alumina, wherein theratio of SiO₂:Al₂O₃ is 90 or less, and wherein the weight ratio ofZSM-48 to alumina is 65:35.
 19. A method for producing a lube basestockand/or a fuel from a feedstock of biological origin, the methodcomprising: contacting the feedstock in the presence of a catalyst toproduce a lube base stock and/or a fuel, wherein the catalyst comprises:a zeolite component selected from ZSM-48, ZSM-23, ZSM-50, ZSM-5, ZSM-22,ZSM-11, ferrierite, faujasite, beta, ZSM-12, MOR, and a mixture thereof,and a hydrogenation component comprising at least three metals selectedfrom the group consisting of Pt, Pd, Ag, Ni, Mo, Co, W, Rh, Re, and Ru,wherein at least one of the at least three metals is in either an oxideor sulfide form.
 20. The method of claim 19, wherein the feedstock ofbiological origin comprises one or more components selected from thegroup consisting of fatty acids, fatty acid esters, fatty alcohols,fatty olefins, mono-glycerides, di-glycerides, tri-glycerides,phospholipids and saccharolipids.
 21. The method of claim 19, whereinthe zeolite is ZSM-48 or ZSM-23; and the hydrogenation componentcomprises (a) Ni, MoOx and WOx or (b) Co, MoOx and WOx, wherein x is inthe range of 0.5 to
 3. 22. The method of claim 19, wherein the catalystcomprises ZSM-48 and a hydrogenation component comprising Ni, MoOx andWOx, wherein x is in the range of 0.5 to 3, wherein the ratio ofSiO₂:Al₂O₃ is 90:1 or less, and wherein the weight ratio of ZSM-48 tothe hydrogenation component is 8:2.
 23. The method of claim 19, whereinthe catalyst further comprises a binder selected from silica, alumina,silica-alumina, titania, zirconia, tantalum oxide, tungsten oxide,molybdenum oxide, vanadium oxide, magnesium oxide, calcium oxide,yttrium oxide, lanthanum oxide, cerium oxide, niobium oxide, titaniumoxide, zirconium oxide, tungstated zirconia, cobalt molybdenum oxide,cobalt molybdenum sulfide, nickel molybdenum oxide, nickel molybdenumsulfide, nickel tungsten oxide, nickel tungsten sulfide, nickelmolybdenum tungsten oxide, nickel molybdenum tungsten sulfide, and amixture thereof.
 24. The method of claim 23, wherein the binder isselected from silica, alumina, silica-alumina, titania, zirconia,yttrium oxide, lanthanum oxide, cerium oxide, niobium oxide, and amixture thereof.